Thermosetting organic resin composition

ABSTRACT

A curable organic resin composition comprising (A) 100 parts by weight of a curable organic resin and (B) 0.01 to 100 parts by weight of a thiocyanato-containing organohydrocarbonoxysilane or an isothiocyanato-containing organohydrocarbonoxysilane represented by the general formula: X—R 1 —Si(OR 2 ) nR 3   3-n  wherein X is NCS— or SCN—, R 1  is an alkylene or alkyleneoxyalkylene group, R 2  and R 3  are monovalent hydrocarbon groups, and the subscript n is 1, 2, or 3. The curable organic resin composition possesses superior moldability and, when cured, exhibits superior adhesive properties on substrates such as metals.

[0001] The present invention relates to a thermosetting organic resincomposition, and, more specifically, to a thermosetting organic resincomposition possessing superior moldability and, when cured, exhibitingsuperior adhesive properties on substrates such as metals.

[0002] It is known that compounding epoxy-containing organosilanes,amine-containing organoalkoxysilanes or mercapto-containingorganoalkoxysilanes with epoxy resins improves their adhesiveproperties. For instance, Japanese Patent Application Publication(Kokai) No. Sho 63-309566 teaches coating material compositions withimproved adhesive properties obtained by compounding silane couplingagents such as 3-glycidoxypropylmethyldiethoxysilane,N-phenyl-3-aminutesopropyltrimethoxysilane, and3-mercaptopropyltrimethoxysilane with epoxy resin powder coatingmaterials.

[0003] Also, Japanese Patent Application Publication (Kokai) No. Hei2-185584 teaches an adhesive agent composition obtained by compounding3-mercaptopropyltrimethoxysilane with an epoxy resin. However, adhesiveproperties of the compositions obtained by the addition ofepoxy-containing alkoxysilanes are not necessarily sufficient forsubstrates such as metals, etc., and, depending on the intended use,such compositions may not be suitable. Furthermore, the originalcurability of the epoxy resins is significantly impaired in compositionsobtained by adding amine-containing organoalkoxysilanes ormercapto-containing organoalkoxysilanes.

[0004] On the other hand, there are also known thiocyanato-containingorganoalkoxysilanes and organic rubber compositions containing saidthiocyanato-containing organoalkoxysilanes. For instance, JapanesePatent Application Publication (Kokai) No. Hei 4-277534 teachescompositions obtained by compounding ethylene-propylene-diene rubber(EPDM) with thiocyanatopropyltrimethoxysilane. After vulcanization inthe presence of organic peroxides, such compositions are said to producerubber moldings exhibiting very little deterioration in physicalproperties and a small compression set.

[0005] In addition, Japanese Patent Application Publication (Kokai) No.Hei 5-214171 teaches vulcanizable organic rubber compositions obtainedby compounding thiocyanatopropyltrimethoxysilane with vulcanizableorganic rubbers, such as natural rubber (NR), styrene-butadiene rubber(SBR), EPDM, etc. When vulcanized in the presence of sulfur, thesecompositions are said to produce rubber moldings exhibiting littledeterioration in physical properties.

[0006] However, there are no known thermosetting organic resincompositions, in which the addition of a thiocyanato-containingorganoalkoxysilane to thermosetting organic resins improves themoldability of said organic resin and its adhesive properties onsubstrates such as metals with which said thermosetting organic resincomposition has contacted.

[0007] As a result of strenuous efforts, the inventors of the presentinvention have discovered that the above-described problems are solvedif epoxy resins are compounded with a thiocyanato-containingorganoalkoxysilane. Furthermore, they have discovered that compounding athiocyanato-containing organoalkoxysilane with thermosetting organicresins, such as phenolic resins, imide resins, etc., results in animprovement in their adhesive properties.

[0008] It is an object of the present invention to provide athermosetting organic resin composition having superior moldability thatcures without impairing the curability of the thermosetting organicresin itself and, when cured, exhibits superior adhesive properties onsubstrates such as metals with which said thermosetting organic resincomposition has contacted.

[0009] The present invention relates to a thermosetting organic resincomposition comprising (A) 100 parts by weight of a thermosettingorganic resin and (B) 0.01 to 100 parts by weight of athiocyanato-containing organohydrocarbonoxysilane or anisothiocyanato-containing organohydrocarbonoxysilane represented by thegeneral formula: X—R¹—Si(OR²)nR³ _(3-n) (wherein X is NCS— or SCN—, R¹is an alkylene or alkyleneoxyalkylene group, R² and R³ are monovalenthydrocarbon groups, and the subscript n is 1, 2, or 3).

[0010] To further explain the above, there are no particular limitationswith regard to the type etc. of the thermosetting organic resin (A) solong as the thermosetting organic resin is liquid or solid at normaltemperatures and cures under beating.

[0011] Epoxy resins, phenolic resins, formaldehyde resins, xyleneresins, xylene-formaldehyde resins, ketone-formaldehyde resins, furanresins, urea resins, imide resins, melamine resins, alkyd resins,unsaturated polyester resins, aniline resins, sulfonamide resins, andsilicone resins are exemplified as such thermosetting organic resins. Ofthe above, epoxy resins, phenolic resins, and imide resins arepreferable.

[0012] Component (B) constitutes an essential characteristic of thecomposition of the present invention and acts to improve moldingproperties of the composition of the present invention and its adhesiveproperties on substrates such as metals.

[0013] Component (B) is a thiocyanato-containingorganohydrocarbonoxysilane or an isothiocyanato-containingorganohydrocarbonoxysilane represented by the general formula:X—R¹—Si(OR²)nR³ _(3-n) (wherein X is NCS— or SCN—, R¹ is an alkylene oralkyleneoxyalkylene group, R² and R³ are monovalent hydrocarbon groups,and the subscript n is 1, 2, or 3).

[0014] In the formula above, the alkylene group of R¹ is exemplified bymethylene, ethylene, methylmethylene, propylene, methylethylene, andbutylene. The alkylenoxyalkylene group of R¹ is exemplified bymethylenoxymethylene, methylenoxyethylene, ethylenoxyethylene, andethylenoxypropylene. R¹ is preferably an alkylene group. The monovalenthydrocarbon groups of R² and R³ are exemplified by methyl, ethyl,n-propyl, i-propyl and other alkyl groups; vinyl, allyl, butenyl andother alkenyl groups; and by phenyl, tolyl, xylyl, and other arylgroups. R² and R³ are preferably alkyl groups. The subscript n is 1, 2,or 3, preferably, 2 and 3.

[0015] The thiocyanato-containing organohydrocarbonoxysilanes, orisothiocyanato-containing organohydrocarbonoxysilanes of Component (B)are exemplified by the following compounds.

[0016] NCS(CH₂)₃Si(OCH₃)₃

[0017] NCS(CH₂)₃Si(OCH₂CH₃)₃

[0018] NCS(CH₂)₃Si[OCH(CH₂)₃]₃

[0019] NCS(CH₂)₃Si[O(CH₂)₂CH₃]₃

[0020] NCS(CH₂)₃Si[O(CH₂)₃CH₃]₃

[0021] NCSCH₂CH(CH₃)CH₂Si(OCH₃)₃

[0022] NCSCH₂CH(CH₃)CH₂Si(OCH₂CH₃)₃

[0023] SCN(CH₂)₃Si(OCH₃)₃

[0024] SCN(CH₂)₃Si(OCH₂CH₃)₃

[0025] SCN(CH₂)₃Si[OCH(CH₃)₂]₃

[0026] SCNCH₂CH(CH₃)CH₂Si(OCH₃)₃

[0027] SCNCH₂CH(CH₃)CH₂Si(OCH₂CH₃)₃

[0028] SCNCH₂CH(CH₃)CH₂Si[OCH(CH₃)₂]₃

[0029] SCNCH₂CH(CH₃)CH₂Si(O(CH₂)₃CH₃)₃

[0030] NCS(CH₂)₃SiCH₃(OCH₃)₂

[0031] NCS(CH₂)₃SiCH₃(OCH₂CH₃)₂

[0032] NCS(CH₂)₃Si(OC₆H₅)₃

[0033] NCSCH2CH(CH₃)CH₂SiCH₃(OCH₃)₃

[0034] Two or more kinds of Component (B) can be added to thecomposition.

[0035] If the amount of Component (B) added to the composition is toosmall, its adhesive properties on substrates such as metals deteriorate,and if it is too large, its mechanical strength decreases. For thisreason, it should be in the range of 0.01 to 100 parts by weight, and,preferably, in the range of 0.1 to 50 parts by weight, per 100 parts byweight of Component (A).

[0036] Although the composition of the present invention comprises theabove-mentioned Component (A) and Component (B), in addition to thesecomponents, various additives known to be compounded with Component (A),for instance, curing agents or cure promoters used to promote the cureof Component (A), fillers, plasticizers, flexibilizers, pigments,heat-stabilizers, flame-retarding agents, antioxidants,photo-sensitizers, organic solvents etc. can be combined therewith.

[0037] Some examples of the curing agents or cure promoters includeprimary or secondary amine compounds, tertiary amine compounds; phtharicanhyride, tetrahydrophtharic anhydride, and other carboxylic acidanhydrides; imidazole compounds; phenolnovlak resin, cresolnovlak resin,and other novlak resins; organoaluminum compounds, organozirconiumcompounds, and other organometallic compounds; phosphine and otherorganic phosphorus compounds; boron complex compounds, organic ammoniumsalts, organic sulfonium salts, organic peroxides, etc.

[0038] The curing agents are added preferably in an amount of 0.1 to 30parts by weight per 100 parts by weight of Component (A), but novlakresins for curing epoxy resins are added preferably in an amount of 10to 400 parts by weight per 100 parts by weight of epoxy resins, and thecure promoters are added preferably in an amount of 0.01 to 10 parts byweight per 100 parts by weight of Component (A).

[0039] The fillers are exemplified by glass fibers, asbestos, aluminafibers, ceramic fibers containing alumina and silica, boron fibers,zirconia fibers, silicon carbide fibers, metal fibers, polyester fibers,aramide fibers, Nylon fibers, phenolic fibers, natural plant and animalfibers and other fibrous fillers; fused silica, precipitated silica,fumed silica, calcined silica, zinc oxide, calcined clay, carbon black,glass beads, alumina, talc, calcium carbonate, clay, aluminum hydroxide,barium sulfate, titanium dioxide, aluminum nitride, silicon carbide,magnesium oxide, beryllium oxide, kaolin, mica, zirconia, and otherpowdery fillers.

[0040] The fillers are added preferably in an amount of 10 to 500 partsby weight per 100 parts by weight of Component (A) in non-liquid curableorganic resin compositions, and in an amount of 0 to 50 parts by weightper 100 parts by weight of Component (A) in liquid curable organic resincompositions.

[0041] Plasticizers and flexibilizers are exemplified by metal salts ofhigher fatty acids, ester waxes, silicone oils, silicone oils containingorganic functional groups, silicone rubbers, and organic rubbers.

[0042] The composition of the present invention comprises theabove-described Component (A) and Component (B) and can be easilyprepared by uniformly mixing them with the above-described additives, ifnecessary. Some examples of equipment used to prepare the composition ofthe present invention include continuous mixer-extruders, Ross mixers,kneader-mixers, twin roll mills, etc. In addition, conventional publiclyknown methods recognized as molding methods suitable for Component (A),such as, for instance, compression molding, transfer molding, injectionmolding, potting, casting, coating, etc., can be utilized in themanufacture of moldings from the composition of the present invention.

[0043] The composition of the present invention as described abovepossesses superior molding properties and, when cured, superior adhesiveproperties on substrates such as metals with which said composition hascontacted. Nickel, copper, brass, iron, steel, stainless steel,aluminum, duralumin, titanium, and silver are exemplified as the metals,and glass, ceramics, stones, and semiconductors are exemplified as thesubstrates. By exploiting the advantages of such properties, it mayprove useful, for instance, for sealing agents, packaging agents,coating agents, adhesive agents etc. used in electric and electroniccomponents or devices, machines, buildings, automobiles etc.

EXAMPLES

[0044] The composition of the present invention is explained in detailbelow by referring to working examples. The term “viscosity,” as used inthe working examples and comparative examples, refers to values obtainedat 25° C. In addition, the moldability, adhesion (adhesive properties),and viscosity change rate of the thermosetting organic resin compositionwere evaluated in accordance with the following methods.

[0045] Moldability

[0046] The moldability of the thermosetting organic resin compositionunder pressure was evaluated by measuring its spiral flow. The spiralflow was measured by a test based on an EMMI standard (EMMI-1-66).

[0047] Adhesion (A)

[0048] An adhesion test piece made up of nickel plates integrally bondedwith a cured product of the thermosetting organic resin composition wasfabricated by sandwiching the thermosetting organic resin compositionbetween two nickel plates (length: 5 cm, width: 1 cm, thickness: 0.5 mm)and conducting compression molding at a specified temperature andspecified pressure. The edges of the two nickel plates of the test piecewere respectively secured in the jig of a tensile tester and pulled awayin a perpendicular direction at a speed of 50 mm/minutes, peeling apartthe nickel plates and the cured product of the thermosetting organicresin composition.

[0049] Subsequently, the condition of the fracture surface between thecured product of the thermosetting organic resin composition and thenickel plates was subjected to visual examination. The results weredesignated in the following manner.

[0050] ⊚: Extremely good adhesion (Fracture occurred in the layer of thecured organic resin. Cohesive failure: 100%).

[0051] ◯: Good adhesion (Partial interface peeling occurred. Cohesivefailure: 95% or more).

[0052] X: Poor adhesion (Peeling occurred at the interface between thecured thermosetting organic resin and the nickel plates. Cohesivefailure: 50% or less)

[0053] Adhesion (B)

[0054] An adhesion test piece made up of nickel plates integrally bondedwith a cured product of the curable organic resin composition wasfabricated by sandwiching the curable organic resin composition betweentwo nickel plates (length: 5 cm, width: 1 cm, thickness: 0.5 mm) andconducting compression molding at a specified temperature and specifiedpressure. In addition, adhesion test pieces made up of copper platesintegrally bonded with a cured product of the curable organic resincomposition were fabricated in the same manner as above.

[0055] The edges of the two nickel plates or the two copper plates ofthese test pieces were respectively secured in the jig of a tensiletester and pulled away in a perpendicular direction at a speed of 50mm/minutes, peeling apart the nickel plates or the copper plates and thecured product of the organic resin composition. The stress required forpeeling was measured and used as the adhesive strength (kgf/cm²).

[0056] Viscosity Change Rate:

[0057] After preparation, the thermosetting organic resin compositionwas allowed to stand at 23° C. for 24 hours. The degree of increase inits viscosity was measured and used as the viscosity change rate.Viscosity change rate=(viscosity of the thermosetting organic resincomposition on standing for 24 hours−viscosity of the curable organicresin composition immediately after preparation)×100/viscosity of thethermosetting organic resin composition immediately after preparation.

Working Example 1

[0058] A curable phenolic resin composition was prepared by kneading 35parts by weight of phenolic resin (phenol-novolak resin Mirex XLC-3Lfrom Mitsui Chemicals, Inc., softening point: 70° C., hydroxylequivalent weight: 170), 3 parts by weight of3-thiocyanatopropyltrimethoxysilane{NCS(CH₂)₃Si(OCH₃)₃}, 65 parts byweight of fused silica powder, 4 parts by weight ofhexamethylenetetramine, and 1 part by weight of carnauba wax using aheating roller at 90° C.

[0059] The composition was finely powdered and the powdered material wassandwiched between two nickel plates (length: 5 cm, width: 1 cm,thickness: 0.5 mm) and subjected to compression molding by heating itfor 3 minutes at a temperature of 175° C. and a pressure of 70 kg/cm².After that, in order to complete the cure, the composition was heatedfor 2 hours at 180° C., producing an adhesion test piece made up ofnickel plates integrally bonded with a cured product of phenolic resin.Using the test piece, the adhesion of the thermosetting organic resincomposition to the nickel plates was measured in accordance with themethod described in Adhesion (A) above, and the results were listed inTable 1.

Comparative Example 1

[0060] A phenol-novolak resin composition was prepared in the samemanner as in Working Example 1, except that3-glycidoxypropyltrimethoxysilane was added instead of the3-thiocyanatopropyltrimethoxysilane used in Working Example 1. Theadhesion of the composition to the nickel plates was measured in thesame manner as in Working Example 1, and the results were listed inTable 1.

Comparative Example 2

[0061] A phenol-novolak resin composition was prepared in the samemanner as in Working Example 1, except that the3-thiocyanatopropyltrimethoxysilane of Working Example 1 was not used.The adhesion of the composition to the nickel plates was measured in thesame manner as in Working Example 1, and the results were listed inTable 1. TABLE 1 Item Working Comparative Comparative Measured Example 1Example 1 Example 2 Adhesion (A) ⊚ X X

Working Example 2

[0062] A thermosetting silicone-epoxy resin composition was prepared bykneading 13 parts by weight of methylphenylpolysiloxane resin consistingof 40 mol % of CH₃SiO_(3/2) units, 10 mol % of C₆H₅(CH₃)SiO_(2/2) units,40 mol % of C₆H₅SiO_(3/2) units, and 10 mol % of (C₆H₅)₂SiO_(2/2) unitsand containing 5 wt % of hydroxyl groups directly bonded to siliconatoms, 13 parts by weight of orthocresol-novolak epoxy resin (EOCN-1020from Nippon Kayaku Co., Ltd., softening point: 80° C., epoxy equivalent:220), 2 parts by weight of 3-thiocyanatopropylmethyldimethoxysilane{NCS(CH₂)₃SiCH₃(OCH₃)₂}, 74 parts by weight of fused silica powder, 0.90parts by weight of aluminum acetylacetonate, and 1 part by weight ofcarnauba wax using a heating roller at 90° C.

[0063] The spiral flow of the thermosetting epoxy resin composition wasmeasured. Next, the thermosetting resin composition was sandwichedbetween two nickel plates (length: 5 cm, width: 1 cm, thickness: 0.5mm), and subjected to compression molding by heating it for 2 minutes ata temperature of 175° C. and a pressure of 70 kg/cm². After that, inorder to complete the cure, the composition was heated for 12 hours at180° C., producing an adhesion test piece made up of nickel platesintegrally bonded with a cured product of the curable organic resincomposition. Using the test piece, the adhesion of the curable organicresin composition to the nickel plates was measured in accordance withthe method described in Adhesion (A) above, and the results were listedin Table 2.

Working Example 3

[0064] A thermosetting epoxy resin composition was prepared in the samemanner as in Working Example 2, except that3-isothiocyanatopropylmethyltrimethoxysilane {SCN(CH₂)₃Si(OCH₃)₃} wasadded instead of the 3-thiocyanatopropylmethyldimethoxysilane used inWorking Example 2. The spiral flow of the composition and its adhesionto the nickel plates were measured in the same manner as in WorkingExample 2, and the results were listed in

Comparative Example 3

[0065] A thermosetting epoxy resin composition was prepared in the samemanner as in Working Example 2, except that3-mercaptopropyltrimethoxysilane {HS(CH₂)₃Si(OCH₃)₃} was added insteadof the 3-thiocyanatopropylmethyldimethoxysilane used in Working Example2. The spiral flow of the composition and its adhesion to the nickelplates were measured in accordance with the method described in Adhesion(A) above, and the results were listed in Table 2.

Comparative Example 4

[0066] A thermosetting epoxy resin composition was prepared in the samemanner as in Working Example 2, except that the3-thiocyanatopropylmethyldimethoxysilane used in Working Example 2 wasnot added. The spiral flow of the composition and its adhesion to thenickel plates were measured in the same manner as in Working Example 2,and the results were listed in Table 2. TABLE 2 Working WorkingComparative Comparative Item Measured Example 2 Example 3 Example 3Example 4 Spiral flow (in.) 42 39 21 13 Adhesion (A) ⊚ ◯ ◯ X

Working Example 4

[0067] A thermosetting polyimide resin composition was prepared bykneading 35 parts by weight of bismaleimidetriazine-type thermosettingpolyimide resin (from Mitsubishi Gas Chemical Co., Ltd.), 4 parts byweight of 3-thiocyanatopropyltrimethoxysilane {NCS(CH₂)₃Si(OCH₃)₃}, 65parts by weight of fused silica powder, 1 part by weight of carnaubawax, and 0.32 parts by weight of aluminum benzoate using a heatingroller at 90° C. The spiral flow of the composition was measured.

[0068] Subsequently, the composition was sandwiched between two nickelplates (length: 5 cm, width: 1 cm, thickness: 0.5 mm) and subjected tocompression molding by heating it for 4 minutes at a temperature of 220°C. and a pressure of 70 kg/cm². After that, in order to complete thecure, the composition was heated for 3 hours at 230° C., producing anadhesion test piece made up of nickel plates integrally bonded with acured product of the thermosetting polyimide resin composition.

[0069] Using the test piece, the adhesion of the thermosetting polyimideresin composition to the nickel plates was measured in accordance withthe method described in Adhesion (A) above, and the results were listedin Table 3.

Comparative Example 5

[0070] A thermosetting polyimide resin composition was prepared in thesame manner as in Working Example 4, except that the3-thiocyanatopropyltrimethoxysilane used in Working Example 4 was notadded. The spiral flow of the composition and its adhesion to the nickelplates were measured in the same manner as in Working Example 4, and theresults were listed in Table 3. TABLE 3 Working Comparative ItemMeasured Example 4 Example 5 Spiral flow (in.) 52 43 Adhesion (A) ⊚ X

Working Example 5

[0071] A thermosetting epoxy resin composition was prepared by kneading75 parts by weight of orthocresol-novolak epoxy resin (EOCN-1020 fromNippon Kayaku Co., Ltd., softening point: 80° C., epoxy equivalent:220), 260 parts by weight of fused silica, 1 part by weight of carnaubawax, 35 parts by weight of phenol-novolak resin (Mirex XLC-3L fromMitsui Chemicals, Inc., softening point: 70° C., hydroxyl equivalentweight: 170), 0.6 parts by weight of triphenylphosphine, and 5 parts byweight of 3-thiocyanatopropyltrimethoxysilane {NCS(CH₂)₃Si(OCH₃)₃} usinga heating roller at 90° C.

[0072] The spiral flow of the composition was measured. Subsequently,the composition was sandwiched between two nickel plates (length: 5 cm,width: 1 cm, thickness: 0.5 mm), and subjected to compression molding byheating it for 3 minutes at a temperature of 150° C. and a pressure of70 kg/cm². After that, in order to complete the cure, the compositionwas heated for 4 hours at 180° C., producing an adhesion test piece madeup of nickel plates integrally bonded with a cured product of thethermosetting epoxy resin composition. Using the test piece, theadhesion of the thermosetting epoxy resin composition to the nickelplates was measured in accordance with the method described in Adhesion(A) above, and the results were listed in Table 4.

Comparative Example 6

[0073] A thermosetting epoxy resin composition was prepared in the samemanner as in Working Example 5, except that3-glycidoxypropyltrimethoxysilane was added instead of the3-thiocyanatopropyltrimethoxysilane used in Working Example 5. Thespiral flow of the composition and its adhesion to the nickel plateswere measured in accordance with the method described in Adhesion (A)above, and the results were listed in Table 4.

Comparative Example 7

[0074] A thermosetting epoxy resin composition was prepared in the samemanner as in Working Example 5, except that the3-thiocyanatopropyltrimethoxysilane used in Working Example 5 was notadded. The spiral flow of the composition and its adhesion to the nickelplates were measured in accordance with the method described in Adhesion(A) above, and the results were listed in Table 4. TABLE 4 WorkingComparative Comparative Item Measured Example 5 Example 6 Example 7Spiral flow (in.) 55 53 52 Adhesion (A) ⊚ X X

Working Example 6

[0075] A thermosetting liquid epoxy resin composition was prepared bythoroughly mixing 20 parts by weight of a liquid epoxy resin (ERL-4221from Union Carbide), 22 parts by weight of liquid acid anhydride (3- and4-methylhexahydrophthalic anhydride), 0.3 parts by weight of tinoctylate, and 2 parts by weight of 3-thiocyanatopropyltrimethoxysilane{NCS(CH₂)₃Si(OCH₃)₃} at room temperature and de-foaming the mixture. Theviscosity change rate of the composition was measured.

[0076] Subsequently, the composition was sandwiched between two nickelplates or two copper plates (length: 5 cm, width: 1 cm, thickness: 0.5mm), and subjected to compression molding by heating it for 3 minutes ata temperature of 120° C. and a pressure of 70 kg/cm². After that, inorder to complete the cure, the composition was heated for 3 hours at150° C., producing an adhesion test piece made up of nickel plates orcopper plates integrally bonded with a cured product of thethermosetting epoxy resin composition. Using the test piece, itsadhesion was measured in accordance with the method described inAdhesion (B) above, and the results were listed in Table 5.

Comparative Example 8

[0077] A thermosetting liquid epoxy resin composition was prepared inthe same manner as in Working Example 6, except that3-mercaptopropyltrimethoxysilane was added instead of the3-thiocyanatopropyltrimethoxysilane used in Working Example 6. Theviscosity change rate and adhesion of the composition were measured inaccordance with the method described in Adhesion (B) above, and theresults were listed in Table 5.

Comparative Example 9

[0078] A thermosetting liquid epoxy resin composition was prepared inthe same manner as in Working Example 6, except that3-glycidoxypropyltrimethoxysilane was added instead of the3-thiocyanatopropyltrimethoxysilane used in Working Example 6. Theviscosity change rate and adhesion of the composition were measured inaccordance with the method described in Adhesion (B) above, and theresults were listed in Table 5.

Comparative Example 10

[0079] A thermosetting epoxy resin composition was prepared in the samemanner as in Working Example 6, except that3-thiocyanatopropyltrimethoxysilane used in Working Example 6 was notadded. The composition was cured in the same manner as in WorkingExample 6. The viscosity change rate and adhesion of the compositionwere measured in accordance with the method described in Adhesion (B)above, and the results were listed in Table 5. TABLE 5 WorkingComparative Comparative Comparative Item Measured Example 6 Example 8Example 9 Example 10 Viscosity  2 Could not be 13  4 change measuredrate (gelling occurred) Adhesion(B) (kg/cm²) Nickel plates 182 85 62 59Copper plates 121 89 52 53

[0080] Because the thermosetting organic resin composition of thepresent invention comprises 100 parts by weight of Component (A) and0.01 to 100 parts by weight of Component (B), i.e. thethiocyanato-containing organohydrocarbonoxysilane orisothiocyanato-containing organohydrocarbonoxysilane represented by thegeneral formula: X—R¹—Si(OR²)nR³ _(3-n) (wherein X is NCS or SCN—, R¹ isan alkylene or alkyleneoxyalkylene group, R² and R³ are monovalenthydrocarbon groups, and the subscript n is 1, 2, or 3), it possessessuperior moldability and, when cured, exhibits superior adhesiveproperties on substrates such as metals with which said thermosettingorganic resin composition has contacted.

1. A curable organic resin composition comprising: (A) 100 parts byweight of a curable organic resin and (B) 0.01 to 100 parts by weight ofa thiocyanato-containing organohydrocarbonoxysilane or anisothiocyanato-containing organohydrocarbonoxysilane represented by thegeneral formula: X—R¹—Si(OR²)nR³ _(3-n) (wherein X is NCS— or SCN—, R¹is an alkylene or allyleneoxyalkylene group, R² and R³ are monovalenthydrocarbon groups, and the subscript n is 1, 2, or 3).
 2. The curableorganic resin composition according to claim 1, wherein Component (A) isa thermosetting organic resin.
 3. The curable organic resin compositionaccording to claim 2, wherein the thermosetting organic resin is a epoxyresin, phenolic resin or imide resin.
 4. The curable organic resincomposition according to claim 1, claim 2 or claim 3, wherein R¹ is analkylene group, R² and R³ are alkyl groups, and the subscript n is 2 or3 in the formula: X—R¹—Si(OR²)nR³ _(3-n) for Component (B).
 5. Thecurable organic resin composition according to claim 4, whereinComponent (B) is 3-thiocyanatopropyltrimethoxysilane,3-thiocyanatopropylmethyldimethoxysilane or3-isothiocyanatopropyltrimethoxysilane.